CN109280321A - A kind of polyoxymethylene film and preparation method thereof - Google Patents

A kind of polyoxymethylene film and preparation method thereof Download PDF

Info

Publication number
CN109280321A
CN109280321A CN201810890956.1A CN201810890956A CN109280321A CN 109280321 A CN109280321 A CN 109280321A CN 201810890956 A CN201810890956 A CN 201810890956A CN 109280321 A CN109280321 A CN 109280321A
Authority
CN
China
Prior art keywords
film
polyoxymethylene
preparation
polyformaldehyde
polyoxymethylene film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810890956.1A
Other languages
Chinese (zh)
Other versions
CN109280321B (en
Inventor
王亚涛
马小丰
李建华
刘莉莉
郭学华
李洪娟
金旺
杨大志
关礼争
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tangshan Kailuan Chemical Technology Co Ltd
Original Assignee
Tangshan Kailuan Chemical Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tangshan Kailuan Chemical Technology Co Ltd filed Critical Tangshan Kailuan Chemical Technology Co Ltd
Priority to CN201810890956.1A priority Critical patent/CN109280321B/en
Priority to PCT/CN2018/110642 priority patent/WO2020029426A1/en
Publication of CN109280321A publication Critical patent/CN109280321A/en
Priority to US16/563,918 priority patent/US20200048452A1/en
Application granted granted Critical
Publication of CN109280321B publication Critical patent/CN109280321B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene

Abstract

The invention discloses a kind of polyoxymethylene film and preparation method thereof, the weight item of polyoxymethylene film composition includes: 96~98 parts of acetal resin, and 0.5~2 part of nucleating agent, 0.5~1 part of antioxidant, formaldehyde absorbent 0.5~1.The characteristic high for polyformaldehyde crystallinity, crystalline rate is fast, using blowing, direct inflation film forming, overcomes drawing process and is also easy to produce thin neck and splintering problem after extruding machine mold melt extrusion, is conducive to polyformaldehyde and forms a film, and is high in machining efficiency, is convenient for industrialization；Copolymerization units-CH will be introduced in polyformaldehyde strand2‑CH2- O-, and its proportion is improved, it can effectively reduce the crystalline rate of material, make it easier for forming a film；Using the multistage air-cooled type of cooling, polyformaldehyde crystallization rate is controlled, prevents part highly crystalline；In conjunction with the application of nucleating agent, spherulite size is promoted to reduce, the tightness for improving crystal regularity and piling up, intermolecular force increases, and the polyoxymethylene film of preparation has excellent surface smoothness.

Description

A kind of polyoxymethylene film and preparation method thereof
Technical field
The present invention relates to a kind of polyoxymethylene films and preparation method thereof, belong to technical field of membrane.
Background technique
Polyformaldehyde as a kind of high crystalline polymer, have excellent mechanical performance, wear resistance, dimensional stability, The excellent properties such as chemical corrosion resistance and self-lubrication.Polyoxymethylene film is prepared by raw material of acetal resin, inherits it poly- Formaldehyde raw material performance is expected to that the polyoxymethylene film that intensity is high, surface is smooth is made, in packaging, building, indoor decoration, medicine etc. It is used widely in field.
But since polyformaldehyde has high crystalline, crystallinity 50-75%, crystallization rate is fast, is easy to shrink generation to the cold Fold, drawing-off are also easy to produce thin neck, thus cause to stretch it is uneven, be easily broken, biaxial tension is difficult.Thus early stage polyformaldehyde is thin Hot-rolling simple tension method is to prepare the important directions of polyoxymethylene film in film research, and patent US3875284 discloses a kind of high Bright polyoxymethylene film and preparation method thereof, the patent prepare polyoxymethylene film using polyformaldehyde as raw material, using hot-rolling pulling method, lead Polyoxymethylene film after stretching is reduced to the 1/1.2-1/6 of former diaphragm thickness, and high light transmission polyoxymethylene film has been made.And for poly- Technological difficulties existing for formaldehyde film biaxial tension, especially after first time stretches, diaphragm crystallizes quickly, stretches and makes to second At difficulty, the prior art mostly uses the method for changing acetal resin ingredient, reduce after crystallinity and crystalline rate again using by Secondary stretch processes；Or synchronous bidirectional stretching technique is used, diaphragm is first prepared, then carry out preheating post-tensioning film forming, but stretch Process is easy to appear thin neck and causes to stretch unevenly, therefore is often also required to improve polyformaldehyde film forming by the way that other auxiliary agents are added Property.Patent US4946930 is prepared for biaxial orientation polyoxymethylene film using two step biaxial tension methods, and the patent is by 1,4-butanediol Diglycidyl ether, metaformaldehyde, hexamethylene copolymerization contain branched polymer, then with polyoxymethylene blended to improve polyformaldehyde Film forming, has been made the smooth polyoxymethylene film in surface, and film surface spherocrystal quantity is at least 50/mm2.Furthermore patent CN201410040912.1, which discloses one kind, has more structure polyformaldehyde nano-porous thin films of micro-nano co-continuous and preparation method thereof, Using polyformaldehyde, polylactic acid as raw material, it is etched into the polyoxymethylene film with porous structure again after mixer melts tabletting, it should The fields such as class perforated membrane can be used for separating, lithium battery diaphragm.
Summary of the invention
The present invention is directed to the problems such as polyformaldehyde film forming is difficult, stretching is easily rupturable, from raw material and prepares two aspects, and one Aspect prepares polyoxymethylene film using blowing one-pass molding, is formed a film, is overcome by inflation direct after extruding machine mold melt extrusion High-crystallinity and crystallization rate give polyformaldehyde film forming bring difficult fastly；On the other hand by improving the ratio of comonomer, Crystalline rate is reduced, extends crystallization time, polyformaldehyde is made to be easier blown film.The type of cooling that blowing uses slow cooling is squeezed out, it is thin Film gradually cools down, crystallization sufficiently, and prevent part be quenched crystallization cause to stretch it is insufficient, in uneven thickness；It is nucleated by introducing Agent, the tightness for promoting nucleus to be uniformly distributed, improve crystal regularity and pile up, conducive to the frictional property for improving film surface Energy.
One of the object of the invention is to provide a kind of polyoxymethylene film, and the weight item composition of the polyoxymethylene film includes: 96~98 parts of acetal resin, 0.5~2 part of nucleating agent, 0.5~1 part of antioxidant, formaldehyde absorbent 0.5~1, preferably total weight Ingredient is 100 parts, and the polyformaldehyde molecular structure is-(CH2-O)n-(CH2-CH2-O)-m, wherein copolymerization units-(CH2-CH2- O)-mMolar ratio is 3%-30%.Wherein acetal resin melt index is 3~13g/10min.Nucleating agent is polytetrafluoroethyl-ne One or both of alkene or Kynoar powder compound.Formaldehyde absorbent be melamine, hexamethylene diamine formaldehyde condensation products, One of dicyandiamide or a variety of compounds.
Antioxidant is conventional antioxidant.
It is another object of the present invention to disclose the preparation method of above-mentioned polyoxymethylene film, comprising the following steps:
(1) polyformaldehyde, nucleating agent, antioxidant, formaldehyde absorbent example in mass ratio are put into high-speed mixer and are mixed It is even, for use.
(2) mixed material is put into extruder hopper, after screw extruder melts, tubulose is extruded by mold Film base.
(3) blowing is used, the tubular film plumular axis squeezed out through mold is to vertically upward, and drawing-off axially upward, simultaneously Bore using compressed air in tubular film base forms a film to inflation, while tubular film embryo outer surface carries out multistage wind using vane Cooling, the tubular film cooled down enter draw roll after herringbone clamping plate, then trimming, winding after being formed, and are finally prepared into To polyoxymethylene film.
Technological parameter: step (2) the extruder feeding temperature is 170~185 DEG C, and plasticization temperature is 190~200 DEG C, Homogenization temperature is 195~210 DEG C, and filter screen temperature is 205~220 DEG C, and mold temperature is 205~220 DEG C, single screw rod host Revolving speed is 40r/min.In step (3) blow-up ratio of film be 1.4~2.5, draw ratio be 2~4, traction roller speed be 12~ 24m/min；When carrying out multistage air-cooled cooling using vane, it is preferred to use 3 grades of slow cooling temperatures are cooled down, along axial bottom-up Temperature is followed successively by 160~140 DEG C, 130~100 DEG C, 80~30 DEG C from high to low；It is preferred that 160~140 DEG C of vane is axially long Degree is 10mm, and 130~100 DEG C of vane axial length is 10mm, 80~30 DEG C of vane axial length is 8mm, wind pressure 0.2 ~0.4MPa.
The technology of the present invention feature and effect:
For polyformaldehyde property of raw material, for the present invention using polyformaldehyde as primary raw material, the method for adopting blown film prepares polyformaldehyde Film, material is squeezed out from cross-head mold, inflation forms a film, multistage air-cooled cooling, a series of changes such as experience viscosity, phase transformation Change, by the reasonable control of the processes such as temperature, inflation, traction, cooling to each section of material, overcomes uneven film thickness, part The problems such as highly crystalline, fold.
The present invention is by adjusting copolymerization units-CH in strand2-CH2The crystallization speed of polyformaldehyde can be changed in-O- proportion Rate, with the promotion of the structure proportion, crystalline rate is gradually decreased, flexible chain extends.But when copolymerization units are more than certain The mechanical property of polyoxymethylene film can be impacted after ratio.
The present invention makes the original big spherocrystal refinement of polyoxymethylene film, size reduces, and improves crystal by the way that nucleating agent is added Regularity and the tightness piled up, can effectively reduce the coefficient of friction of polyoxymethylene film.
The nucleating agent that the present invention uses has excellent frictional behaviour, part is not for polytetrafluoroethylene (PTFE) or Kynoar It can improve the surface smoothness of material as the auxiliary agent of nucleus, reduce coefficient of friction.
The present invention introduces simultaneously for polyformaldehyde process window is narrow, stability is poor, is also easy to produce the material characteristics of zip mode decomposition Improve copolymerization units-CH2-CH2- O- proportion can improve the thermal stability of polyformaldehyde；And oxygen under high temperature is inhibited by antioxidant Change and decomposes；And formaldehyde absorbent is introduced, content of formaldehyde in control system prevents it from melt feed further being promoted to decompose, effectively Property of raw material is kept, and reduces deterioration of the blown film in the process to processing environment.
The characteristics of blowing that the present invention uses has larger difference, blowing compared with squeezing out pulling method is to melt polyformaldehyde Body is passed through the direct inflation film forming of compressed air after squeezing out, and keeps film crystallization time more abundant by the way that multistage is air-cooled, is conducive to improve Crystallinity reduces coefficient of friction.
Detailed description of the invention
Fig. 1 is the spherulite size picture for the polyformaldehyde that copolymerization units account for 10%.
The spherulite size picture after nucleating agent is added for the polyformaldehyde that copolymerization units account for 10% by Fig. 2.
Fig. 3 is crystallinity-time graph of the polyformaldehyde of copolymerization units containing different proportion.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1: this polyoxymethylene film uses following raw material proportionings and preparation method.
The weight item composition of polyoxymethylene film includes: 98 parts of acetal resin, and 1 part of Kynoar, antioxidant 0.5 Part, 0.5 part of melamine, in the polyformaldehyde molecular structure-(CH2-CH2-O)-mStructure proportion is 3%.
The preparation method of polyoxymethylene film the following steps are included:
(1) be the polyformaldehyde raw material of 13g/10min by melt index, Kynoar, antioxidant, melamine press quality Ratio is put into high-speed mixer and is uniformly mixed, for use.
(2) mixed material is put into extruder hopper, after screw extruder melts, pipe is extruded by mold Shape film base.
(3) blowing is used, the upward drawing-off of tubulose polyformaldehyde film embryo squeezed out through mold, and be blown into using compressed air Film, while multistage air-cooled cooling is carried out using outer surface vane, the tubular film cooled down enters draw roll after herringbone clamping plate, Trimming, winding after being formed again, is finally prepared polyoxymethylene film.
Technological parameter: extruder feeding temperature is 170~185 DEG C in step (2), and plasticization temperature is 190~200 DEG C, Changing temperature is 195~210 DEG C, and filter screen temperature is 205~220 DEG C, and mold temperature is 205~220 DEG C, and screw speed is 40r/min；In step (3) blow-up ratio be 1.4, draw ratio 2, traction roller speed be 12m/min, 3 grades of slow cooling temperatures by height to Low to be followed successively by 160 DEG C, 130 DEG C, 80 DEG C, vane axial length is respectively 10mm, 10m, 8mm, wind pressure 0.4MPa.
2 polyoxymethylene films of embodiment use following raw material proportionings and preparation method.
The weight item composition of polyoxymethylene film includes: 97.5 parts of acetal resin, and 0.5 part of Kynoar, antioxidant 1 Part, 0.5 part of melamine, 0.5 part in dicyandiamide, copolymerization units-(CH in the polyformaldehyde molecular structure2-CH2-O)-mIt is shared Ratio is 10%.
The preparation method of polyoxymethylene film the following steps are included:
(1) be the polyformaldehyde raw material of 9g/10min by melt index, Kynoar, antioxidant, melamine press quality Ratio is put into high-speed mixer and is uniformly mixed, for use.
(2) mixed material is put into extruder hopper, after screw extruder melts, tubulose is extruded by mold Film base.
(3) blowing is used, the upward drawing-off of tubulose polyformaldehyde film embryo squeezed out through mold, and be blown into using compressed air Film, while multistage air-cooled cooling is carried out using outer surface vane, the tubular film cooled down enters draw roll after herringbone clamping plate, Trimming, winding after being formed again, is finally prepared polyoxymethylene film.
Technological parameter: feeding temperature is 170~185 DEG C in step (2), and plasticization temperature is 190~200 DEG C, homogenization temperature It is 195~210 DEG C, filter screen temperature is 205~220 DEG C, and mold temperature is 205~220 DEG C, and single screw rod engine speed is 40r/ min；Blow-up ratio is 2 in step (3), draw ratio 3, and traction roller speed is 18 m/min, and 3 grades of slow cooling temperatures are from high to low successively For 150 DEG C, 120 DEG C, 60 DEG C, vane axial length is respectively 10m, 10mm, 8mm, wind pressure 0.2MPa.
3 polyoxymethylene films of embodiment use following raw material proportionings and preparation method.
The weight item composition of polyoxymethylene film includes: 96 parts of acetal resin, and 1 part of polytetrafluoroethylene (PTFE), Kynoar 1 Part, 1 part of antioxidant, 1 part of hexamethylene diamine formaldehyde condensation products, the polyformaldehyde molecular structure copolymerization units-(CH2-CH2-O)-mIt is shared Ratio is 20%.
A kind of preparation method of high barrier polyoxymethylene film, comprising the following steps:
(1) polyformaldehyde raw material, polytetrafluoroethylene (PTFE), antioxidant, the hexamethylene diamine formaldehyde condensation polymer for being 3g/10min by melt index Object example in mass ratio is put into high-speed mixer and is uniformly mixed, for use.
(2) mixed material is put into extruder hopper, after screw extruder melts, tubulose is extruded by mold Film base.
(3) blowing is used, the upward drawing-off of tubulose polyformaldehyde film embryo squeezed out through mold, and blown upwards using compressed air It is expanded into film, while multistage air-cooled cooling is carried out using outer surface vane, the tubular film cooled down enters after herringbone clamping plate to be led Roller is stretched, then trimming, winding after being formed, polyoxymethylene film is finally prepared.
Technological parameter: feeding temperature is 170~185 DEG C in step (1), and plasticization temperature is 190~200 DEG C, homogenization temperature It is 195~210 DEG C, filter screen temperature is 205~220 DEG C, and mold temperature is 205~220 DEG C, and single screw rod engine speed is 40r/ min；In step (2) blow-up ratio be 2.5, draw ratio 4, traction roller speed be 24m/min, 3 grades of slow cooling temperatures from high to low according to It is secondary be 150 DEG C, 100 DEG C, 30 DEG C, vane axial length is respectively 10mm, 10mm, 8mm, wind pressure 0.4MPa.
4 polyoxymethylene films of embodiment use following raw material proportionings and preparation method.
The weight item composition of polyoxymethylene film includes: 96 parts of acetal resin, and 1 part of polytetrafluoroethylene (PTFE), Kynoar 1 Part, 1 part of antioxidant, 1 part of hexamethylene diamine formaldehyde condensation products, the polyformaldehyde molecular structure copolymerization units-(CH2-CH2-O)-mIt is shared Ratio is 30%.
A kind of preparation method of high barrier polyoxymethylene film, comprising the following steps:
(1) polyformaldehyde raw material, polytetrafluoroethylene (PTFE), antioxidant, the hexamethylene diamine formaldehyde condensation polymer for being 3g/10min by melt index Object example in mass ratio is put into high-speed mixer and is uniformly mixed, for use.
(2) mixed material is put into extruder hopper, after screw extruder melts, tubulose is extruded by mold Film base.
(3) blowing is used, the upward drawing-off of tubulose polyformaldehyde film embryo squeezed out through mold, and blown upwards using compressed air It is expanded into film, while multistage air-cooled cooling is carried out using outer surface vane, the tubular film cooled down enters after herringbone clamping plate to be led Roller is stretched, then trimming, winding after being formed, polyoxymethylene film is finally prepared.
Technological parameter: feeding temperature is 170~185 DEG C in step (1), and plasticization temperature is 190~200 DEG C, homogenization temperature It is 195~210 DEG C, filter screen temperature is 205~220 DEG C, and mold temperature is 205~220 DEG C, and single screw rod engine speed is 40r/ min；In step (2) blow-up ratio be 2.5, draw ratio 4, traction roller speed be 24m/min, 3 grades of slow cooling temperatures from high to low according to It is secondary be 140 DEG C, 100 DEG C, 30 DEG C, vane axial length is respectively 10mm, 10mm, 8mm, wind pressure 0.4MPa.
The polyoxymethylene film performance indicator of preparation of the embodiment of the present invention is shown in Table 1.
1 polyoxymethylene film performance indicator of table
Performance indicator Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Film thickness/μm 300 140 30 30
Film thickness average deviation/% ±13 ±11 ±10 ±9
Dynamic friction coefficient 0.16 0.13 0.11 0.11
Transverse tensile strength/MPa 76 83 113 108
Longitudinal tensile strength/MPa 78 91 98 93
Influence of the copolymerization units proportion to polyformaldehyde flexible chain is as shown in table 2.
The flexible chain of 2 polyformaldehyde of copolymerization units containing different proportion of table
Sample 3% 10% 15% 20% 30%
t1/2(S) 115 121 132 135 142

Claims (10)

1. a kind of preparation method of polyoxymethylene film, which is characterized in that the weight item composition of the polyoxymethylene film includes: poly- 96~98 parts of formaldehyde resin, 0.5~2 part of nucleating agent, 0.5~1 part of antioxidant, formaldehyde absorbent 0.5~1, the polyformaldehyde tree Rouge molecular structure is-(CH2-O)n-(CH2-CH2-O)-m, wherein copolymerization units-(CH2-CH2-O)-mShared molar ratio is 3%- 30%；Method includes the following steps:
(1) polyformaldehyde, nucleating agent, antioxidant, formaldehyde absorbent example in mass ratio are put into high-speed mixer and are uniformly mixed, to With；
(2) mixed material is put into extruder hopper, after screw extruder melts, tubular film is extruded by mold Base；
(3) blowing is used, the upward drawing-off of tubulose polyformaldehyde film base squeezed out through mold, and formed a film using compressed air inflation, Multistage air-cooled cooling is carried out using outer surface vane simultaneously, the tubular film cooled down enters draw roll after herringbone clamping plate, then Trimming, winding, are finally prepared polyoxymethylene film after being formed.
2. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: in the step (2), squeeze Machine feeding temperature is 170~185 DEG C out, and plasticization temperature is 190~200 DEG C, and homogenization temperature is 195~210 DEG C, filter screen temperature It is 205~220 DEG C, mold temperature is 205~220 DEG C, screw speed 40r/min.
3. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: thin in the step (3) The blow-up ratio of film is 1.4~2.5, and draw ratio is 2~4, and traction roller speed is 12~24m/min.
4. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: more in the step (3) Grade is air-cooled using the slow cooling for being not less than 3 grades, along axial bottom-up temperature by height gradually to low.
5. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: in the step (3), 3 Grade slow cooling temperature is followed successively by 160~140 DEG C, 130~100 DEG C, 80~30 DEG C from high to low.
6. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: in the step (3), 3 The vane axial length of preferably 160~140 DEG C of vane of slow cooling of grade is 10mm, 130~100 DEG C of vane axial length be 10mm, 80~30 DEG C of vane axial length is 8mm, and wind pressure is 0.2~0.4MPa.
7. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: the acetal resin is molten Melting index is 3~13g/10min.
8. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: the nucleating agent is poly- four One or both of vinyl fluoride or Kynoar powder compound.
9. a kind of preparation method of polyoxymethylene film according to claim 1, it is characterised in that: the formaldehyde absorbent is One of melamine, hexamethylene diamine formaldehyde condensation products, dicyandiamide or a variety of compounds.
10. the polyoxymethylene film that -9 described in any item methods are prepared according to claim 1.
CN201810890956.1A 2018-08-07 2018-08-07 Polyformaldehyde film and preparation method thereof Active CN109280321B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201810890956.1A CN109280321B (en) 2018-08-07 2018-08-07 Polyformaldehyde film and preparation method thereof
PCT/CN2018/110642 WO2020029426A1 (en) 2018-08-07 2018-10-17 Polyformaldehyde thin film and preparation method therefor
US16/563,918 US20200048452A1 (en) 2018-08-07 2019-09-08 Polyoxymethylene film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810890956.1A CN109280321B (en) 2018-08-07 2018-08-07 Polyformaldehyde film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109280321A true CN109280321A (en) 2019-01-29
CN109280321B CN109280321B (en) 2020-01-21

Family

ID=65182990

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810890956.1A Active CN109280321B (en) 2018-08-07 2018-08-07 Polyformaldehyde film and preparation method thereof

Country Status (2)

Country Link
CN (1) CN109280321B (en)
WO (1) WO2020029426A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3875284A (en) * 1972-09-25 1975-04-01 Asahi Chemical Ind Process for preparing clear polyoxymethylene film
CN88101745A (en) * 1987-04-01 1988-11-23 聚塑料株式会社 Method of manufacturing polyacetal resin film
CN106367954A (en) * 2016-10-17 2017-02-01 杭州师范大学 Ag-nanoparticle-containing polyformaldehyde/polylactic acid (POM/PLLA) composite fiber membrane and preparation method thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63344A (en) * 1986-05-29 1988-01-05 ヘキスト・セラニーズ・コーポレーション High abrasion resistance high impact strength polyacetal polymer
DE3834547A1 (en) * 1988-10-11 1990-04-19 Basf Ag POLYOXYMETHYLENE MOLDING MATERIALS WITH IMPROVED THERMAL STABILITY, METHOD FOR THE PRODUCTION AND USE THEREOF
JPH0545865A (en) * 1991-08-12 1993-02-26 Asahi Chem Ind Co Ltd Film for protecting photomask
DE102004051214A1 (en) * 2004-10-20 2006-05-04 Basf Ag Flowable polyoxymethylenes
KR101535398B1 (en) * 2006-12-04 2015-07-08 미츠비시 가스 가가쿠 가부시키가이샤 Oxymethylene copolymer composition for stretching material, stretching material, structures, and process for producing the same
US8188169B2 (en) * 2008-08-29 2012-05-29 E. I. Du Pont De Nemours And Company Polyoxymethylene compositions and articles made from these
US20110223486A1 (en) * 2010-03-12 2011-09-15 Xiaomin Zhang Biaxially oriented porous membranes, composites, and methods of manufacture and use
CN102181137A (en) * 2011-03-24 2011-09-14 山东省意可曼科技有限公司 High-performance PHAs (polyhydroxyalkanoates)/POM (polyoxymethylene)/PLA (polylactic acid) blending alloy
JP6329478B2 (en) * 2014-11-13 2018-05-23 旭化成株式会社 Process for producing polyacetal copolymer
CN105175982B (en) * 2015-10-19 2018-08-28 云南云天化股份有限公司 A kind of acetal resin and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3875284A (en) * 1972-09-25 1975-04-01 Asahi Chemical Ind Process for preparing clear polyoxymethylene film
CN88101745A (en) * 1987-04-01 1988-11-23 聚塑料株式会社 Method of manufacturing polyacetal resin film
CN106367954A (en) * 2016-10-17 2017-02-01 杭州师范大学 Ag-nanoparticle-containing polyformaldehyde/polylactic acid (POM/PLLA) composite fiber membrane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王玉琦等: "《塑料材料》", 31 August 1993 *

Also Published As

Publication number Publication date
WO2020029426A1 (en) 2020-02-13
CN109280321B (en) 2020-01-21

Similar Documents

Publication Publication Date Title
US20220097274A1 (en) Method and device for directly preparing foamed polylactic acid (pla) product from pla melt
CN102276948B (en) Preparation method of biaxially stretched polyvinyl fluoride film
CN101838445A (en) PETG blow molding film and preparation method thereof
CN108530752B (en) Micro-foaming continuous long glass fiber reinforced polypropylene composite material and preparation method and application thereof
CN107936430A (en) High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof
CN103085219B (en) Microporous foamed rubber-plastic heat insulation product and preparation method thereof
CN1009653B (en) Polyacrylic microporous barrier and preparation process thereof
CN103789869A (en) Method for producing flat filaments by using PET (Polyethylene Terephthalate)
CN109720066B (en) Polyvinyl alcohol/polypropylene composite film and preparation method thereof
CN113549323B (en) High-strength high-fluidity low-warpage long glass fiber reinforced polyamide composite material and preparation method and application thereof
CN104908329A (en) Preparation method for high-crystallinity bidirectional high-mechanical strength polylactic acid film
CN103030891A (en) Long glass fiber-reinforced polypropylene composite material and preparation method thereof
CN111454517B (en) Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof
CN111808387A (en) Polyvinyl chloride mulching film and preparation method thereof
CN107722550B (en) A kind of polyoxymethylene film and preparation method thereof
CN105479707B (en) A kind of preparation method of activeness and quietness PLA
CN103009750B (en) A kind of Biaxially oriented polypropylene common cigarette packaging film and manufacture method thereof
EP0287246A2 (en) Method of manufacturing polybutylene terephthalate resin films
CN109280321A (en) A kind of polyoxymethylene film and preparation method thereof
CN109280273B (en) High melt strength polypropylene film compositions and films and uses thereof
CN109265825B (en) Polypropylene or polypropylene compound foamed product and preparation method thereof
CN105128370A (en) Preparation method of high-flexibility BOPP (Biaxially-oriented Polypropylene) film
CN115216125A (en) Special anti-broken PET spinning weather-resistant master batch and preparation method thereof
CN112936899A (en) Production method of multifunctional high-haze transfer film
CN1297386C (en) Method for producing two-way stretching polypropylene film for cigarette by pipe soaking method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant